Copolymers of vinyl halides



PATENT OFFIC 2,361,504 COPOLYMERS OF VINYL HALIDES Winfield Scott, Akron, Ohio, and Raymond B. Seymour, Allentown, Pa assignors to Wingl'oot Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application January 17, 1940, Serial No. 314,265

4 Claims. (Cl. 260-86) This invention relates to copolymers of vinyl above can be varied as mentioned. In the folhalides, specifically, of vinyl chloride and vinyl lowing table are given the results obtained with bromide, and to methods of preparing the same. various proportions, each of the copolymers be- It is known that a polymerized material may ing soluble in ethylene dichloride: be made from vinyl chloride, the same being 5 known as polyvinyl chloride, but this substance, as obtained by emulsion polymerization, 0011- $33,, tains but a small proportion of material which is soluble in ethylene dichloride. It has now been found that an inclusion of vinyl bromide with the monomeric vinyl chloride results in copolymers which are readily soluble in ethylene dichloride and in other similar solvents. Furthermore, polymers containing larger amounts of the bromide are more easily soluble in such soll5 vents than those containmg smaller amounts of the bromide. While vinyl chloride has been It was observed that vinyl bromide polypolymerized by itself and likewise vinyl bromide, merizes more slowly than vinyl chloride and, also, and each has been copolymerized with various that mixtures of vinyl chloride and vinyl bromide other monomeric substances, no attempt has been containing a, large amount of the latter polymade, apparently,to copolymerize these two sub merize more slowly than when lesser amounts stances together. Hence, the solubilizing efiect -.of the bromide are present. A consequence of of vinyl bromidein these polymerized vinyl halide this is that lower yields in a given time will be mixtures has not previously been observed. obtained as the proportion of vinyl bromide is The eiiect may be obtained with various increased and, therefore, the yield values given amounts of the vinyl bromide, proportions from above cannot be taken as absolute. That is to 5 to 90% of vinyl bromide having yielded useful say, satisfactory yields of high bromide copolymaterials. Correspondingly, the vinyl chloride mers may be obtained by merely continuing the may be present from 95 to 10% on the total polymerization for a longer time. weight of monomers present. Other monomers Of course, it will be understood that the conor modifying agents may also be included in the ditions given in the foregoing exam-pie may be resulting products, in which case the ratios of varied. Other emulsifying agents may be used Vinyl Yield, bromide per cent vinyl bromide and vinyl chloride are maintained in place of Aquarex D, such as Gardinol WA,

on a basis of the total vinyl halides present. Wetanol, Nekal B X and Sulfatate, since it is A typical preparation of copolymers of vinyl only necessary that efiective emulsification of chloride and vinyl bromide is the following, the the monomers be obtained. Likewise, other proportions of the halides being varied as desired. temperatures may be employed, a range of 25 To fifteen c. c. of a 5% solution of an emulsifyto 80 C. being practicable in most instances. ing agent, such as Aquarex D (the sodium salt Also, the hydrogen ion concentration can be of the sulphate mono esters of higher fatty alco- 40 varied, values from pH6 to pH9 being used and hols) is added a. butler mixture, such as even lower pH values if the proper emulsifier is McIlvaine buffer, which gives a hydrogen ion conemployed. Furthermore, the mixed vinyl halides centration of approximately pH'Z. To this is may be polymerized in the mass, a temperature then added 1.6 grams of carbon tetrachloride, 0.2 of 25 to 80 C. being suitable in this procedure gram of sodium perborate and 25 grams of the also, and a catalyst of the peroxide type, such as desired mixture of monomers of vinyl chloride benzoyl peroxide, being employed to increase and vinyl bromide. Polymerization is carried the rate of reaction. out with agitation at a temperature of 35 C. The copolymers obtained were found to be .and is complete in from 20 to 90 hours. The solids in every instance where the polymerizapolymer is obtained from the latex thus formed tion had proceeded far enough and all of the by the addition of alcohol or by salting out. The samples were readily soluble in such solvents as solid is then washed free of bullet and emulsifyethylene dichloride, chlorbenzene, methyl chloing agent and dried. reform, and the like. This property of solu- The ratio of monomeric vinyl chloride and I bility 'in these solvents renders the copolymers vinyl bromide employed in the procedure given suitable for making films and for impregnation and lamination of fabrics. They may also be substituted for rubber in a number of its applications and especially where oil resistance is desired.

While there have been described above certain preierred embodiments of the invention it will be understood that the invention is not limited thereto but that numerous modifications may be made therein within the scope of the appended claims, wherein it is intended to cover all features of patentable novelty residing in the invention.

We claim:

l. Polymerized materials comprising copolymerized vinyl chloride and vinyl bromide containing from 5 to 90% by weight of the vinyl bromide polymerized to a. degree which would render the vinyl chloride insoluble in ethylene dichloride if polymerized alone.

2. A copolymer of about to 30 percent by weight of vinyl bromide and about 90 to 70 percent by weight of vinyl chloride polymerized to a degree which would render the vinyl chloride insoluble in ethylene dichloride if polymerized one.

3. An ethylene-dichloride-soluble material comprising copolymerized vinyl chloride and vinyl bromide containing from E. to 90% by weight of the vinyl bromide polymerized to a. degree which would render the vinyl chloride insoluble in ethylene dichloride if polymerized alone. 7

4. An ethylene dichloride soluble material comprising a copolymer of about by weight of vinyl bromide and about by weight of vinyl chloride polymerized together to a. degree which would render the vinyl chloride insoluble in ethylene dichloride if polymerized alone.

WINFIEID SCO'IT. RAYMOND B. SEYMOUR. 

